Compositions comprising 2,3,3,3-tetrafluoropropene and hydrocarbons and uses thereof

ABSTRACT

The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises 2,3,3,3-tetrafluoropropene (HFC-1234yf) and at least one hydrocarbon. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, and aerosol propellants.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit of U.S. Provisional PatentApplication No. 61/116,041, filed Nov. 19, 2008.

BACKGROUND

1. Field of the Disclosure

The present disclosure relates to compositions for use in refrigeration,air-conditioning, and heat pump systems wherein the compositioncomprises a tetrafluoropropene and at least one hydrocarbon. Thecompositions of the present invention are useful in processes forproducing cooling or heat, as heat transfer fluids, foam blowing agents,aerosol propellants, and fire suppression and fire extinguishing agents.

2. Description of Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134abeing the most widely used at this time, have zero ozone depletionpotential and thus are not affected by the current regulatory phase outas a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase outof certain HFC refrigerants. Currently, the automobile industry isfacing regulations relating to global warming potential for refrigerantsused in mobile air-conditioning. Therefore, there is a great currentneed to identify new refrigerants with reduced global warming potentialfor the mobile air-conditioning market. Should the regulations be morebroadly applied in the future, for instance for stationary airconditioning and refrigeration systems, an even greater need will befelt for refrigerants that can be used in all areas of the refrigerationand air-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a includeHFC-152a, pure hydrocarbons such as butane or propane, or “natural”refrigerants such as CO₂. Many of these suggested replacements aretoxic, flammable, and/or have low energy efficiency. New replacementsare also being proposed for HCFC-22, R404A, R407C, R410A among others.Therefore, new alternative refrigerants are being sought.

BRIEF SUMMARY

The object of the present disclosure is to provide novel refrigerantcompositions and heat transfer fluid compositions that provide uniquecharacteristics to meet the demands of low or zero ozone depletionpotential and lower global warming potential as compared to currentrefrigerants.

Disclosed herein are compositions comprising:

-   -   HFO-1234yf and cyclopropane;    -   HFO-1234yf and propylene;    -   HFO-1234yf, HFC-152a, and cyclopropane;    -   HFO-1234yf, HFC-152a, and propane; and    -   HFO-1234yf, HFC-134a, and cyclopropane.

Also disclosed herein are processes to produce cooling and heating andmethods of replacing other refrigerants.

DETAILED DESCRIPTION

Before addressing details of embodiments described below, some terms aredefined or clarified.

DEFINITIONS

As used herein, the term heat transfer composition means a compositionused to carry heat from a heat source to a heat sink.

A heat source is defined as any space, location, object or body fromwhich it is desirable to add, transfer, move or remove heat. Examples ofheat sources is spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air-conditioning, industrial water chillers orthe passenger compartment of an automobile requiring air-conditioning.In some embodiments, the heat transfer composition may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). In other embodiments, evaporative cooling processes mayutilize heat transfer compositions as well.

A heat sink is defined as any space, location, object or body capable ofabsorbing heat. A vapor compression refrigeration system is one exampleof such a heat sink.

A heat transfer system is the system (or apparatus) used to produce aheating or cooling effect in a particular space. A heat transfer systemmay be a mobile system or a stationary system.

Examples of heat transfer systems included but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,heat pumps, mobile refrigerators, mobile air conditioning units andcombinations thereof.

As used herein, mobile heat transfer system refers to any refrigeration,air conditioner, or heating apparatus incorporated into a transportationunit for the road, rail, sea or air. In addition, mobile refrigerationor air conditioner units, include those apparatus that are independentof any moving carrier and are known as “intermodal” systems. Suchintermodal systems include “container' (combined sea/land transport) aswell as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems that arefixed in place during operation. A stationary heat transfer system maybe associated within or attached to buildings of any variety or may bestand alone devices located out of doors, such as a soft drink vendingmachine. These stationary applications may be stationary airconditioning and heat pumps (including but not limited to chillers, hightemperature heat pumps, residential, commercial or industrial airconditioning systems, and including window, ductless, ducted, packagedterminal, chillers, and those exterior but connected to the buildingsuch as rooftop systems). In stationary refrigeration applications, thedisclosed compositions may be useful in equipment including commercial,industrial or residential refrigerators and freezers, ice machines,self-contained coolers and freezers, flooded evaporator chillers, directexpansion chillers, walk-in and reach-in coolers and freezers, andcombination systems. In some embodiments, the disclosed compositions maybe used in supermarket refrigeration systems. Additionally, stationarysystems include secondary loop systems that utilize a primaryrefrigerant and a secondary heat transfer fluid.

Refrigeration capacity (also referred to as cooling capacity) is a termto define the change in enthalpy of a refrigerant in an evaporator perpound of refrigerant circulated, or the heat removed by the refrigerantin the evaporator per unit volume of refrigerant vapor exiting theevaporator (volumetric capacity). The refrigeration capacity is ameasure of the ability of a refrigerant or heat transfer composition toproduce cooling. Therefore, the higher the capacity, the greater thecooling that is produced. Cooling rate refers to the heat removed by therefrigerant in the evaporator per unit time.

Coefficient of performance (COP) is the amount of heat removed dividedby the required energy input to operate the cycle. The higher the COP,the higher is the energy efficiency. COP is directly related to theenergy efficiency ratio (EER) that is the efficiency rating forrefrigeration or air conditioning equipment at a specific set ofinternal and external temperatures.

The term “subcooling” is meant the reduction of the temperature of aliquid below that liquid's saturation point for a given pressure. Thesaturation point is the temperature at which a vapor composition iscompletely condensed to a liquid (also referred to as the bubble point).But subcooling continues to cool the liquid to a lower temperatureliquid at the given pressure. By cooling a liquid below the saturationtemperature, the net refrigeration capacity can be increased. Subcoolingthereby improves refrigeration capacity and energy efficiency of asystem. Subcool amount is the amount of cooling below the saturationtemperature (in degrees) or how far below its saturation temperature aliquid composition is cooled.

Superheat is a term that defines how far above its saturation vaportemperature (the temperature at which, if the composition is cooled, thefirst drop of liquid is formed, also referred to as the “dew point”) avapor composition is heated.

Temperature glide (sometimes referred to simply as “glide”) is theabsolute value of the difference between the starting and endingtemperatures of a phase-change process by a refrigerant within acomponent of a refrigerant system, exclusive of any subcooling orsuperheating. This term may be used to describe condensation orevaporation of a near azeotrope or non-azeotropic composition.

By azeotropic composition is meant a constant-boiling mixture of two ormore substances that behave as a single substance. One way tocharacterize an azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has the samecomposition as the liquid from which it is evaporated or distilled,i.e., the mixture distills/refluxes without compositional change.Constant-boiling compositions are characterized as azeotropic becausethey exhibit either a maximum or minimum boiling point, as compared withthat of the non-azeotropic mixture of the same compounds. An azeotropiccomposition will not fractionate within a refrigeration or airconditioning system during operation, which may reduce heat transfer andefficiency of the system. Additionally, an azeotropic composition willnot fractionate upon leakage from a refrigeration or air conditioningsystem.

A near-azeotropic composition (also commonly referred to as an“azeotrope-like composition”) is a substantially constant boiling liquidadmixture of two or more substances that behaves essentially as a singlesubstance. One way to characterize a near-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas substantially the same composition as the liquid from which it wasevaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition isnear-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isless than about 10 percent.

A non-azeotropic composition is a mixture of two or more substances thatbehaves as a simple mixture rather than a single substance. One way tocharacterize a non-azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has a substantiallydifferent composition as the liquid from which it was evaporated ordistilled, that is, the admixture distills/refluxes with substantialcomposition change. Another way to characterize a non-azeotropiccomposition is that the bubble point vapor pressure and the dew pointvapor pressure of the composition at a particular temperature aresubstantially different. Herein, a composition is non-azeotropic if,after 50 weight percent of the composition is removed, such as byevaporation or boiling off, the difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent of the original composition has been removed is greater thanabout 10 percent.

As used herein, the term “lubricant” means any material added to acomposition or a compressor (and in contact with any heat transfercomposition in use within any heat transfer system) that provideslubrication to the compressor to aid in preventing parts from seizing.

As used herein, compatibilizers are compounds which improve solubilityof the hydrofluorocarbon of the disclosed compositions in heat transfersystem lubricants. In some embodiments, the compatibilizers improve oilreturn to the compressor. In some embodiments, the composition is usedwith a system lubricant to reduce oil-rich phase viscosity.

As used herein, oil-return refers to the ability of a heat transfercomposition to carry lubricant through a heat transfer system and returnit to the compressor. That is, in use, it is not uncommon for someportion of the compressor lubricant to be carried away by the heattransfer composition from the compressor into the other portions of thesystem. In such systems, if the lubricant is not efficiently returned tothe compressor, the compressor will eventually fail due to lack oflubrication.

As used herein, “ultra-violet” dye is defined as a UV fluorescent orphosphorescent composition that absorbs light in the ultra-violet or“near” ultra-violet region of the electromagnetic spectrum. Thefluorescence produced by the UV fluorescent dye under illumination by aUV light that emits at least some radiation with a wavelength in therange of from 10 nanometers to about 775 nanometers may be detected.

Global warming potential (GWP) is an index for estimating relativeglobal warming contribution due to atmospheric emission of a kilogram ofa particular greenhouse gas compared to emission of a kilogram of carbondioxide. GWP can be calculated for different time horizons showing theeffect of atmospheric lifetime for a given gas. The GWP for the 100 yeartime horizon is commonly the value referenced. For mixtures, a weightedaverage can be calculated based on the individual GWPs for eachcomponent.

Ozone depletion potential (ODP) is a number that refers to the amount ofozone depletion caused by a substance. The ODP is the ratio of theimpact on ozone of a chemical compared to the impact of a similar massof CFC-11 (fluorotrichloromethane). Thus, the ODP of CFC-11 is definedto be 1.0. Other CFCs and HCFCs have ODPs that range from 0.01 to 1.0.HFCs have zero ODP because they do not contain chlorine.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a composition,process, method, article, or apparatus that comprises a list of elementsis not necessarily limited to only those elements but may include otherelements not expressly listed or inherent to such composition, process,method, article, or apparatus. Further, unless expressly stated to thecontrary, “or” refers to an inclusive or and not to an exclusive or. Forexample, a condition A or B is satisfied by any one of the following: Ais true (or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method or apparatus that includes materials, steps,features, components, or elements, in addition to those literallydisclosed provided that these additional included materials, steps,features, components, or elements do materially affect the basic andnovel characteristic(s) of the claimed invention. The term ‘consistingessentially of’ occupies a middle ground between “comprising” and‘consisting of’:

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of:”

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the disclosed compositions,suitable methods and materials are described below. All publications,patent applications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

Compositions

Disclosed are compositions comprising 2,3,3,3-tetrafluoropropene(HFO-1234yf) and at least one other compound. HFO-1234yf may be made bymethods known in the art.

In one embodiment, in the compositions of the present inventioncomprising HFO-1234yf the other compound comprises at least onehydrocarbon. In another embodiment, in the compositions of the presentinvention comprising HFO-1234yf the other compound comprises at leastone hydrocarbon selected from the group consisting of propane,cyclopropane and propylene.

In another embodiment the disclosed compositions also contain otherfluorinated compounds selected from the group consisting oftetrafluoroethane, pentafluoroethane (HFC-125), and difluoroethane(1,1-difluoroethane or HFC-152a). Tetrafluoroethane may be1,1,1,2-tetrafluoroethane (HFC-134a) or 1,1,2,2-tetrafluoroethane(HFC-134). These fluorinated compounds are commercially available or maybe made by methods known in the art.

In one embodiment, compositions are disclosed comprising:

-   -   HFO-1234yf and cyclopropane;    -   HFO-1234yf and propylene;    -   HFO-1234yf, HFC-152a, and cyclopropane;    -   HFO-1234yf, HFC-152a, and propane; and    -   HFO-1234yf, HFC-134a, and cyclopropane.

The compositions disclosed herein are useful as heat transfercompositions, aerosol propellant, foaming agents, blowing agents,carrier fluids, displacement drying agents, buffing abrasion agents,polymerization media, expansion agents for polyolefins and polyurethane,and gaseous dielectrics. In liquid or gaseous form, and the disclosedcompositions act as a working fluid used to carry heat from a heatsource to a heat sink. Such heat transfer compositions may also beuseful as a refrigerant in a cycle wherein the fluid undergoes phasechanges; that is, from a liquid to a gas and back or vice versa.

In one embodiment the disclosed binary compositions may be generallyuseful when the HFO-1234yf is present at about 1 weight percent to about99 weight percent. In another embodiment, the useful compositionscomprise about 20 weight percent to about 99 weight percent HFO-1234yf.In another embodiment, the useful compositions comprise about 40 weightpercent to about 98 weight percent HFO-1234yf. And in yet anotherembodiment, the useful compositions comprise about 50 weight percent toabout 98 weight percent HFO-1234yf.

In one embodiment, the disclosed ternary compositions containingHFO-1234yf, hydrocarbon and an additional fluorocarbon may be generallyuseful when the HFO-1234yf is present at about 1 weight percent to about98 weight percent of the overall composition. In another embodiment, theuseful compositions comprise about 20 weight percent to about 98 weightpercent tetrafluoropropene. In another embodiment, the usefulcompositions comprise about 40 weight percent to about 98 weight percenttetrafluoropropene. And in yet another embodiment, the usefulcompositions comprise about 50 weight percent to about 98 weight percenttetrafluoropropene.

In one embodiment, the disclosed compositions are generally expected tomaintain the desired properties and functionality when the componentsare present in the concentrations as listed +/−2 weight percent.

In some embodiments, the disclosed compositions are found to benear-azeotropic. Near-azeotropic compositions comprising2,3,3,3-tetrafluoropropene have been identified at the specifiedtemperature as listed in Table 1.

TABLE 1 Near-azeotrope range Temp Components (weight percent) (° C.)HFO-1234yf/cyclopropane 1-99/99-1 25 HFO-1234yf/propylene 1-86/99-14 and95-99/5-1 25 HFO-1234yf/HFC-152a/cyclopropane 1-98/1-98/1-98 25HFO-1234yf/HFC-152a/propane 1-98/1-98/20-98 0HFO-1234yf/HFC-134a/cyclopropane 1-98/1-98/1-98 25

In some embodiments, the disclosed compositions are found to beazeotropic. Azeotropic compositions comprising2,3,3,3-tetrafluoropropene have been identified at the specifiedtemperature as listed in Table 2.

TABLE 2 Composition Concentration, wt % Temp, Pressure, (A/B/C) A B C °C. psia (Kpa) HFO-1234yf/cyclopropane 65.4 34.6 25 123.8HFO-1234yf/propylene 23.9 76.1 25 167.7 HFO-1234yf/152a/ 52.6 11.1 36.325 124.4 cyclopropane HFC-1234yf/152a/propane 18.2 27.5 54.3 0 76.0

Certain of the compositions of the present invention are non-azeotropiccompositions.

A non-azeotropic composition may have certain advantages over azeotropicor near azeotropic mixtures. A non-azeotropic composition is a mixtureof two or more substances that behaves as a mixture rather than a singlesubstance. One way to characterize a non-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas a substantially different composition as the liquid from which itwas evaporated or distilled, that is, the admixture distills/refluxeswith substantial composition change. Another way to characterize anon-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially different. Herein, a composition isnon-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isgreater than about 10 percent.

In some embodiments, in addition to the HFO-1234yf, hydrocarbons, andoptional additional fluorinated compounds, the disclosed compositionsmay comprise optional other components.

In some embodiments, the optional other components (also referred toherein as additives) in the compositions disclosed herein may compriseone or more components selected from the group consisting of lubricants,dyes, solubilizing agents, compatibilizers, stabilizers, tracers,perfluoropolyethers, anti wear agents, extreme pressure agents,corrosion and oxidation inhibitors, metal surface energy reducers, metalsurface deactivators, free radical scavengers, foam control agents,viscosity index improvers, pour point depressants, detergents, viscosityadjusters, and mixtures thereof. Indeed, many of these optional othercomponents fit into one or more of these categories and may havequalities that lend themselves to achieve one or more performancecharacteristic.

In some embodiments, one or more additive is present in the compositionsdisclosed in small amounts relative to the overall composition. In someembodiments, the amount of additive(s) concentration in the disclosedcompositions is from less than about 0.1 weight percent to as much asabout 5 weight percent of total additive. In some the additives arepresent in the disclosed compositions in an amount between about 0.1weight percent to about 3.5 weight percent. The additive component(s)selected for the disclosed composition is selected on the basis of theutility and/or individual equipment components or the systemrequirements.

In some embodiments, the disclosed compositions include at least onelubricant selected from the group consisting of mineral oils (oils ofmineral origin), synthetic lubricants, and mixtures thereof.

In some embodiments, the disclosed compositions include at least onelubricant selected from those suitable for use with refrigeration orair-conditioning equipment. In some embodiments, the disclosedcompositions include at least one synthetic oil selected from thosereadily known in the field of compression refrigeration lubrication.

In some embodiments, at least one optional component is a mineral oillubricant. In some embodiments, the mineral oil lubricant is selectedfrom the group consisting of paraffins (including straight carbon chainsaturated hydrocarbons, branched carbon chain saturated hydrocarbons,and mixtures thereof), naphthenes (including saturated cyclic and ringstructures), aromatics (those with unsaturated hydrocarbons containingone or more ring, wherein one or more ring is characterized byalternating carbon-carbon double bonds) and non-hydrocarbons (thosemolecules containing atoms such as sulfur, nitrogen, oxygen and mixturesthereof), and mixtures and combinations of thereof.

Some embodiments may contain one or more synthetic lubricant. In someembodiments, the synthetic lubricant is selected from the groupconsisting of alkyl substituted aromatics (such as benzene ornaphthalene substituted with linear, branched, or mixtures of linear andbranched alkyl groups, often generically referred to as alkylbenzenes),synthetic paraffins and naphthenes, poly (alpha olefins), polyglycols(including polyalkyene glycols), dibasic acid esters, polyesters,neopentyl esters, polyvinyl ethers (PVEs), silicones, silicate esters,fluorinated compounds, phosphate esters and mixtures and combinationsthereof.

In some embodiments, the compositions as disclosed herein furthercomprise at least one lubricant selected from the group consisting ofmineral oils, alkylbenzenes, polyalphaolefins, polyalkylene glycols,polyol esters, polyvinyl ethers, and mixtures thereof.

In some embodiments, the compositions disclosed herein contain at leastone commercially available lubricant. In some embodiments thecompositions disclosed herein contain at least one lubricant selectedfrom the group consisting of BVM 100 N (paraffinic mineral oil sold byBVA Oils), Suniso® 1GS, Suniso® 3GS and Suniso® 5GS (naphthenic mineraloils sold by Crompton Co.), Sontex® 372LT (naphthenic mineral oil soldby Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by CalumetLubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenessold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold byNippon Oil), polyol esters (POEs) such as Castrol® 100 (Castrol, UnitedKingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (DowChemical, Midland, Mich.), and mixtures thereof.

In some embodiments, the lubricant is present in an amount of less than5.0 weight % to the total composition. In other embodiments, the amountof lubricant is between about 0.1 and 3.5 weight % of the totalcomposition.

Notwithstanding the above weight ratios for compositions disclosedherein, it is understood that in some heat transfer systems, while thecomposition is being used, it may acquire additional lubricant from oneor more equipment component of such heat transfer system. For example,in some refrigeration, air conditioning and heat pump systems,lubricants may be charged in the compressor and/or the compressorlubricant sump. Such lubricant would be in addition to any lubricantadditive present in the refrigerant in such a system. In use, therefrigerant composition when in the compressor may pick up an amount ofthe equipment lubricant to change the refrigerant-lubricant compositionfrom the starting ratio.

In such heat transfer systems, even when the majority of the lubricantresides within the compressor portion of the system, the entire systemmay contain a total composition with as much as about 75 weight percentto as little as about 1.0 weight percent of the composition beinglubricant. In one embodiment, in some systems, for example supermarketrefrigerated display cases, the system may contain about 3 weightpercent lubricant (over and above any lubricant present in therefrigerant composition prior to charging the system) and 97 weightpercent refrigerant. In another embodiment, in some systems, for examplemobile air conditioning systems, the system may contain about 20 weightpercent lubricant (over and above any lubricant present in therefrigerant composition prior to charging the system) and about 80weight percent refrigerant.

In some embodiments, the disclosed compositions may include additives toreduce the flammability characteristics of the composition. Hydrocarbonrefrigerants are known to be flammable compounds and in someapplications, the reduction of the flammability characteristics isdesired. Additives that may be included in the disclosed compositionsinclude, salts (e.g. acetates, borates, carbonates, bicarbonates,phosphates, nitrates, hydroxides, oxides, molybdates, bromides,bromates, chlorates, chlorides, or iodides), phosphorous compoundsincluding phosphate esters, organic phosphonates, and phosphonium salts,boric acid, organic boron compounds, brominated compounds, chlorinatedparaffins, ammonium polyphosphates, melamines, mixtures of water withpolyalkylene glycols or polyol esters, perfluorinated lubricants,fluoroketones, fluoroiodo compounds, or mixtures thereof.

Representative salts for reducing flammability include but are notlimited to: sodium acetate (CH₃CO₂Na), potassium acetate (CH₃CO₂K),potassium carbonate (K₂CO₃), iron (II) carbonate (FeCO₃), sodiumcarbonate (Na₂CO₃), ammonium carbonate ((NH₄)₂CO₃), sodium bicarbonate(NaHCO₃), potassium bicarbonate, (KHCO₃), ammonium phosphate((NH₄)₃PO₄), potassium nitrate (KNO₃), sodium chloride (NaCl), potassiumchloride (KCl), cobalt chloride (CoCl₂), rubidium chloride (RbCl),titanium chloride (TiCl₄), sodium bromide (NaBr), potassium bromide(KBr), rubidium bromide (RbBr), potassium iodide (KI), rubidium iodide(RbI), magnesium hydroxide (Mg(OH)₂), aluminum hydroxide (Al(OH)₃), zincborate (3ZnO:2B₂O₃), zinc oxide (ZnO), zinc molybdate (ZnMoO₄), calciummolybdate (CaMoO₄), copper oxides, (Cu₂O and CuO), and antimony oxides,including but not limited to antimony trioxide (Sb₂O₃) and antimonypentoxide (Sb₂O₅), and others. Such salts are available from manychemical suppliers such as Aldrich, Milwaukee, Wis.

In some embodiments, the compositions as disclosed herein may furthercomprise phosphorus compounds for reducing flammability including butnot limited to phosphate esters, including but not limited to: trialkylphosphates, triaryl phosphates, mixed alkyl-aryl phosphates(alkyldiaryl, dialkylaryl or alkylated aryl), and cyclic phosphates.Representative trialkyl phosphates include: trimethyl phosphate((CH₃)₃PO₄); triethyl phosphate ((CH₃CH₂)₃PO₄); tributyl phosphate((C₄H₉)₃PO₄); trioctyl phosphate ((C₈H₁₇)₃PO₄); andtri(2-ethylhexyl)phosphate ((CH₃CH(C₂H₅)(CH₂)₄)₃PO₄). Representativetriaryl phosphates include: triphenyl phosphate ((C₆H₅O)₃PO); tricresylphosphate (TCP, (CH₃C₆H₄O)₃PO); and trixylenyl phosphate(((CH₃)₂O₆H₃O)₃PO). Representative mixed alkyl-aryl phosphates include:isopropylphenyl phenyl phosphate (IPPP, (C₆H₅O)₂((CH₃)₂CHO)PO) andbis(t-butylphenyl)phenyl phosphate (TBPP, (C₆H₅O)₂((CH₃)₃C)PO). Suchphosphorus compounds are available from multiple chemical suppliers suchas Aldrich (Milwaukee, Wis.); Alfa Aesar (Ward Hill, Mass.); or AkzoNobel (Arnhem, the Netherlands). Additional representative phosphoruscompounds are Syn-O-Ad 8784, a butylated triphenyl phosphate from AkzoNobel (Arnhem, the Netherlands); Durad 620, a tert-butylated triphenylphosphate from Great Lakes Chemical Corporation (GLCC, West Lafayette,Ind.); and Durad 220 and 110, iso-propylated triphenyl phosphates alsofrom GLCC.

In some embodiments, the disclosed compositions may further organicphosphonates and phosphonium salts for reducing flammability includingbut not limited to: tris monochloropropyl phosphate (TMCPP, differentisomers, tris(2-chloroisopropyl)phosphate, andtris(2-chloropropyl)phosphate); tris (1,3-dichloro-2-propyl)phosphate(TDCPP, P(OCH₂OH)₄Cl); dimethyl phosphonate (PHO(OCH₃)₂); andtetrakis(hydroxymethyl)phosphonium chloride (P(CH₂OH)₄Cl) among others.These phosphorus compounds are also available from Aldrich, Alfa Aesar,or Akzo Nobel.

In some embodiments, the disclosed compositions may further compriseboron compounds such as boric acid (H₃BO₃), triphenyl borane (B(C₆H₅)₃)and other boron salts, such as sodium borate.

In some embodiments, the disclosed compositions may further comprisebrominated organic compounds such as hexabromocyclododecane ordecabromodiphenyl oxide. The brominated organic compounds furtherinclude aliphatic compounds such as dibromoneopentyl glycol (DBNPG,C(CH₂Br)₂(CH₂OH)₂, Specialchem FR-522); trisbromoneopentyl phosphate(Specialchem FR-370/FR-372, (C(CH₂Br)₃CH₂O)PO), trisbromoneopentylalcohol (TBNPA, CH₂(CH₂Br)OH), and hexabromocyclododecane (HBCD,cyclo-(—CHBrCHBrCH₂CH₂CHBrCHBrCH₂CH₂CHBrCHBrCH₂CH₂—)).

The brominated organic compounds further include aromatic compounds suchas decabromodiphenyl oxide (DECA, O(C₆Br₅)₂, Specialchem FR-1210);tris(tribromophenyl)triazine (Specialchem FR-245); tetrabromobisphenol Abis(2,3-dibromopropyl ether) (Specialchem FR-720); Octabromodiphenyloxide (OCTA, Specialchem FR-1208); tetrabromobisphenol A(CH₃)₂C(C₆H₂Br₂OH)₂, Specialchem FR-1524); and brominatedtrimethylphenyl indan (Specialchem FR-1808).

The brominated organic compounds that function as flammability reducingadditives in the compositions as disclosed herein include brominatedepoxy compounds such as Specialchem F-2016 (oligomer), among others. Allof the aliphatic brominated, aromatic brominated and brominated epoxycompounds listed above are available from Specialchem S. A. (Paris,France).

In some embodiments, the compositions as disclosed herein may furthercomprise chlorinated paraffins with 10-30 carbon atoms and having fromabout 35 weight percent to about 70 weight percent chlorine in themolecule. Chlorinated paraffins include those sold under the trademarks:Chlorez®/Hordaresin® flame retardant additives; Doversperse® dispersionsand emulsions of resinous and liquid chlorinated paraffins; Doverguard®brominated chlorinated paraffins; Paroil®; and Chlorowax® liquidchlorinated paraffins; by Dover Chemical Corporation (Dover, Ohio).Additionally, chlorinated paraffins of the present invention includecompounds sold under the trademarks: Cereclor® 42, 42SS, 48, 70, LCCP44, and 46 fire retardant chlorinated paraffin waxes and Cereclor® S-45,51 L, S-52, S-52HV, S-55, S-56, S-56B, and MCCP 54 C₁₄-C₁₇ chlorinatedparaffins, by Pioneer (Houston, Tex.).

In some embodiments, the compositions as disclosed herein may furthercomprise ammonium polyphosphates (APPS), [NH₄PO₃]_(n) as flammabilityreducing additives. The ammonium polyphosphates may be straight chainedor branched and cross-linked molecules. Ammonium polyphosphates areavailable coated with silanes, melamines or other substances. Thepresent invention is intended to include coated or uncoated ammoniumpolyphosphate formulations. Representative of these APP formulations areFR CROS 484 (uncoated), RF CROS 486 (surface reacted silane coating),and FR CROS 484 (surface reacted melamine coating), which are allavailable from Specialchem S. A. (Paris, France).

In some embodiment, the compositions as disclosed herein may furthercomprise mixtures of water with polyalkylene glycols (PAGs) or polyolester (POEs) lubricants optionally with anti corrosion, antiwear,stabilizer and/or lubricity additives, as flammability reducingadditives. The formulations with water may comprise 30 weight percentwater or more, such as those sold under the trademark EMKAROX® HV 45 andEMKAROX® HV 20 (PAGs) bu Uniqema, Gouda, The Netherlands. As thePAG/water and POE/water as described may also function as a lubricant,additional lubricants may not be necessary. Alternatively, additionallubricants may be added to the PAG/water or POE/water mixtures as may berequired for lubrication.

In some embodiments, the compositions as disclosed herein may furthercomprise perfluorocarbon or perfluoropolyether lubricants asflammability reducing additives. Examples include but are not limited toperfluoropolyethers sold under the trademarks: Krytox® (DuPont,Wilmington, Del.); Fomblin® (Solvay Solexis, Italy); and Demnum™(offered by Daikin America, Inc., Osaka, Japan). Representativelubricants of this type are Krytox® 1531XP or Krytox® GLP series,Fomblin® Z-Dol, Z-Tetraol, AM 2001, or AM 3001, Demnum™ LR-200 or S-65and other Demnum™ oils. As said perfluorinated lubricants may alsofunction as a lubricant, no other lubricant may be required in acomposition containing said perfluorinated fire hazard-reducing agents.Alternatively, the perfluorinated lubricants may be included as anadditive to the other lubricants as described herein.

In some embodiments, the compositions as disclosed herein may furthercomprise melamines as flammability reducing additives. Such melaminesinclude melamine (2,4,6-triamino-1,3,5-triazine) and homologues andderivatives of melamine. Such melamine homologues include multi-ringstructures such as melam(1,3,5-triazine-2,4,6-triamine-n-(4,6-diamino-1,3,5-triazine-2-yl),melem (2,5,8-triamino-1,3,4,6,7,9,9b-heptaazaphenalene), and melon(poly[8-amino-1,3,4,6,7,9,9b-heptaazaphenalene-2,5-diyl)]). Suchmelamine derivatives include melamine cyanurate and melamine(mono/pyro/poly) phosphates, such as those melamines sold under thetrademark Melapur® MP (melamine monophosphate and Melapur® 200 (amelamine polyphosphate) by Specialchem S. A. (Paris, France).

In some embodiments, the compositions disclosed herein may furthercomprise fluoroketones as flammability reducing additives, wherein saidfluoroketones are represented by the formula R¹COR², wherein R¹ and R²are independently selected from straight or branched chain, saturated orunsaturated, aliphatic or alicyclic partially or fully fluorinatedhydrocarbon radicals. Additionally, R¹ and R² may be joined to form acyclic fluoroketone ring. The fluoroketones may contain from about 2 to10 carbon atoms. Preferred fluoroketones contain 4 to 8 carbon atoms.The fluoroketones of the present invention may further containheteroatoms, such as oxygen, thus forming additional ketone groups,ether groups, aldehyde groups, or ester groups. Examples of suchfluoroketones are1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone orperfluoroethyl isopropyl ketone (PEIK);1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone orperfluoromethyl isopropyl ketone (PMIK);1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3-pentanone;1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; and1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone.PEIK is available from 3M™ (St. Paul, Minn.) and the other fluoroketoneslisted may be prepared as described in U.S. Pat. Nos. 3,185,734 and6,478,979 incorporated herein by reference, and J. Am. Chem. Soc., vol84, pp. 4285-88, 1962.

In some embodiments, the compositions as disclosed herein may furthercomprise fluoroiodo compounds such as trifluoromethyl iodide (CF₃I), asflammability reducing additives.

The concentration of the flammability reducing additives will varydepending upon the flammability characteristics of the composition towhich these additives will be added. The concentration of theflammability reducing additives in any of the disclosed compositions maybe sufficient to reduce flammability to an acceptable level or eliminatethe flammability of said composition entirely. In one embodiment, theconcentration of flammability reducing additive with respect to thedisclosed compositions may be from about greater than zero weightpercent to about 50 weight percent based on the total composition. Inanother embodiment the concentration of flammability reducing additivewill be from about 0.1 weight percent to about 20 weight percent. In yetanother embodiment, the concentration of the flammability reducingadditive will be from about 0.1 weight percent to about 5 weight percentbased on the total composition.

In some embodiments, the disclosed compositions include at least onedye. In some embodiments, the disclosed compositions include at leastone ultra-violet (UV) dye.

In some embodiments, the disclosed compositions include at least one UVdye that is a fluorescent dye. In some embodiments, the describedcompositions include at least one UV dye that is a fluorescent dyeselected from the group consisting of naphthalimides, perylenes,coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins, and derivatives of said dye andcombinations thereof.

In some embodiments, the disclosed compositions contain from about 0.001weight percent to about 1.0 weight percent UV dye. In other embodiments,the UV dye is present in an amount of from about 0.005 weight percent toabout 0.5 weight percent; and in other embodiments, the UV dye ispresent in an amount of from 0.01 weight percent to about 0.25 weightpercent of the total composition.

In some embodiments, the UV dye is a useful component for detectingleaks of the composition by permitting one to observe the fluorescenceof the dye at or in the vicinity of a leak point in an apparatus (e.g.,refrigeration unit, air-conditioner or heat pump). One may observe theUV emission, e.g., fluorescence from the dye under an ultra-violetlight. Therefore, if a composition containing such a UV dye is leakingfrom a given point in an apparatus, the fluorescence can be detected atthe leak point, or in the vicinity of the leak point.

In some embodiments, the described compositions further contain at leastone solubilizing agent selected to improve the solubility of one or moredye in the disclosed compositions. In some embodiments, the weight ratioof dye to solubilizing agent ranges from about 99:1 to about 1:1.

In some embodiments, solubilizing agents in the disclosed compositionsinclude at least one compound selected from the group consisting ofhydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (such asdipropylene glycol dimethyl ether), amides, nitriles, ketones,chlorocarbons (such as methylene chloride, trichloroethylene,chloroform, or mixtures thereof), esters, lactones, aromatic ethers,fluoroethers and 1,1,1-trifluoroalkanes and mixtures thereof.

In some embodiments, at least one compatibilizer is selected to improvethe compatibility of one or more lubricant with the disclosedcompositions. In some embodiments, the compatibilizer is selected fromthe group consisting of hydrocarbons, hydrocarbon ethers,polyoxyalkylene glycol ethers (such as dipropylene glycol dimethylether), amides, nitriles, ketones, chlorocarbons (such as methylenechloride, trichloroethylene, chloroform, or mixtures thereof), esters,lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, andmixtures thereof.

In some embodiments, one or more solubilizing agent and/orcompatibilizer is selected from the group consisting of hydrocarbonethers consisting of the ethers containing only carbon, hydrogen andoxygen, such as dimethyl ether (DME) and mixtures thereof.

In some embodiments, the disclosed composition includes at least onelinear or cyclic aliphatic or aromatic hydrocarbon compatibilizercontaining from 5 to 15 carbon atoms. In some embodiments, thecompatibilizer is selected from the group consisting of at least onehydrocarbon; in other embodiments, the compatibilizer is a hydrocarbonselected from the group consisting of at least pentane, hexane, octane,nonane, decane, commercially available from Exxon Chemical (USA) underthe trademarks Isopar® H (a high purity C₁₁ to C₁₂ iso-paraffinic),Aromatic 150 (a C₉ to C₁₁ aromatic), Aromatic 200 (a C₉ to C₁₅ aromatic)and Naptha 140 and mixtures thereof.

In some embodiments, the disclosed compositions include at least onepolymeric compatibilizer. In some embodiments, the disclosedcompositions include at least one a polymeric compatibilizer selectedfrom those that are random copolymers of fluorinated and non-fluorinatedacrylates, wherein the polymer comprises repeating units of at least onemonomer represented by the formulae CH₂═C(R¹)CO₂R², CH₂═C(R³)C₆H₄R⁴, andCH₂═C(R⁵)C₆H₄XR⁶, wherein X is oxygen or sulfur; R¹, R³, and R⁵ areindependently selected from the group consisting of H and C₁-C₄ alkylradicals; and R², R⁴, and R⁶ are independently selected from the groupconsisting of carbon-chain-based radicals containing C, and F, and mayfurther contain H, Cl, ether oxygen, or sulfur in the form of thioether,sulfoxide, or sulfone groups and mixtures thereof. Examples of suchpolymeric compatibilizers include those commercially available from E.I. du Pont de Nemours & Co. (Wilmington, Del., 19898, USA) under thetrademark Zonyl® PHS. Zonyl® PHS is a random copolymer made bypolymerizing 40 weight percent CH₂═C(CH₃)CO₂CH₂CH₂(CF₂CF₂)_(m)F (alsoreferred to as Zonyl® fluoromethacrylate or ZFM) wherein m is from 1 to12, primarily 2 to 8, and 60 weight percent lauryl methacrylate(CH₂═C(CH₃)CO₂(CH₂)₁₁CH₃, also referred to as LMA).

In some embodiments, the compatibilizer component contains from about0.01 to 30 weight percent (based on total amount of compatibilizer) ofan additive which reduces the surface energy of metallic copper,aluminum, steel, or other metals and metal alloys thereof found in heatexchangers in a way that reduces the adhesion of lubricants to themetal. Examples of metal surface energy reducing additives include thosecommercially available from DuPont under the trademarks Zonyl® FSA,Zonyl® FSP, and Zonyl® FSJ.

In some embodiments, the disclosed compositions further include metalsurface deactivators. In some embodiments, at least one metal surfacedeactivator is selected from the group consisting of areoxalyl bis(benzylidene) hydrazide (CAS reg no. 6629-10-3),N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS reg no.32687-78-8),2,2,′-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CASreg no. 70331-94-1), N,N′-(disalicyclidene)-1,2-diaminopropane (CAS regno. 94-91-7) and ethylenediaminetetra-acetic acid (CAS reg no. 60-00-4)and its salts, and mixtures thereof.

In some embodiments, the compositions disclosed herein further includeat least one stabilizer selected from the group consisting of hinderedphenols, thiophosphates, butylated triphenylphosphorothionates, organophosphates, or phosphites, aryl alkyl ethers, terpenes, terpenoids,epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols,lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalic acid, diphenylterephthalic acid, ionic liquids, and mixtures thereof.

In some embodiments, said at least one stabilizer is selected from thegroup consisting of tocopherol; hydroquinone; t-butyl hydroquinone;monothiophosphates; and dithiophosphates, commercially available fromCiba Specialty Chemicals, Basel, Switzerland, hereinafter “Ciba”, underthe trademark Irgalube® 63; dialkylthiophosphate esters, commerciallyavailable from Ciba under the trademarks Irgalube® 353 and Irgalube®350, respectively; butylated triphenylphosphorothionates, commerciallyavailable from Ciba under the trademark Irgalube® 232; amine phosphates,commercially available from Ciba under the trademark Irgalube® 349(Ciba); hindered phosphites, commercially available from Ciba asIrgafos® 168 and Tris-(di-tert-butylphenyl)phosphite, commerciallyavailable from Ciba under the trademark Irgafos® OPH; (Di-n-octylphosphite); and iso-decyl diphenyl phosphite, commercially availablefrom Ciba under the trademark Irgafos® DDPP; trialkyl phosphates, suchas trimethyl phosphate, triethylphosphate, tributyl phosphate, trioctylphosphate, and tri(2-ethylhexyl)phosphate; triaryl phosphates includingtriphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate; andmixed alkyl-aryl phosphates including isopropylphenyl phosphate (IPPP),and bis(t-butylphenyl)phenyl phosphate (TBPP); butylated triphenylphosphates, such as those commercially available under the trademarkSyn-O-Ad® including Syn-O-Ad® 8784; tert-butylated triphenyl phosphatessuch as those commercially available under the trademark Durad®620;isopropylated triphenyl phosphates such as those commercially availableunder the trademarks Durad® 220 and Durad® 110; anisole;1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene;myrcene, alloocimene, limonene (in particular, d-limonene); retinal;pinene; menthol; geraniol; farnesol; phytol; Vitamin A; terpinene;delta-3-carene; terpinolene; phellandrene; fenchene; dipentene;caratenoids, such as lycopene, beta carotene, and xanthophylls, such aszeaxanthin; retinoids, such as hepaxanthin and isotretinoin; bornane;1,2-propylene oxide; 1,2-butylene oxide; n-butyl glycidyl ether;trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane;3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd);3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co.,Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212(Toagosei Co., Ltd); ascorbic acid; methanethiol (methyl mercaptan);ethanethiol (ethyl mercaptan); Coenzyme A; dimercaptosuccinic acid(DMSA); grapefruit mercaptan((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine((R)-2-amino-3-sulfanyl-propanoic acid); lipoamide(1,2-dithiolane-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3(or3,4)-dimethylphenyl]-2(3H)-benzofuranone, commercially available fromCiba under the trademark Irganox® HP-136; benzyl phenyl sulfide;diphenyl sulfide; diisopropylamine; dioctadecyl 3,3′-thiodipropionate,commercially available from Ciba under the trademark Irganox® PS 802(Ciba); didodecyl 3,3′-thiopropionate, commercially available from Cibaunder the trademark Irganox® PS 800;di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, commercially availablefrom Ciba under the trademark Tinuvin® 770;poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate,commercially available from Ciba under the trademark Tinuvin® 622LD(Ciba); methyl bis tallow amine; bis tallow amine;phenol-alpha-naphthylamine; bis(dimethylamino)methylsilane (DMAMS);tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane;vinyltrimethoxysilane; 2,5-difluorobenzophenone;2′,5′-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone;benzyl phenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionicliquids; and mixtures and combinations thereof.

In some embodiments, the disclosed composition includes at least oneionic liquid stabilizer selected from the group consisting of organicsalts that are liquid at room temperature (approximately 25° C.), thosesalts containing cations selected from the group consisting ofpyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium,pyrazolium, thiazolium, oxazolium and triazolium and mixtures thereof;and anions selected from the group consisting of [BF₄]—, [PF₆]—,[SbF₆]—, [CF₃SO₃]—, [HCF₂CF₂SO₃]—, [CF₃HFCCF₂SO₃]—, [HCClFCF₂SO₃]—,[(CF₃SO₂)₂N]—, [(CF₃CF₂SO₂)₂N]—, [(CF₃SO₂)₃C]—, [CF₃CO₂]—, and F— andmixtures thereof. In some embodiments, e ionic liquid stabilizers areselected from the group consisting of emim BF₄(1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF₄(1-butyl-3-methylimidazolium tetraborate); emim PF₆(1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF₆(1-butyl-3-methylimidazolium hexafluorophosphate), all of which areavailable from Fluka (Sigma-Aldrich).

In some embodiments, at least one stabilizer is a hindered phenol, whichare any substituted phenol compound including phenols comprising one ormore substituted or cyclic, straight chain, or branched aliphaticsubstituent group, such as, alkylated monophenols including2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinoneand alkylated hydroquinones including t-butyl hydroquinone, otherderivatives of hydroquinone; and the like, hydroxylated thiodiphenylethers, including 4,4′-thio-bis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tertbutylphenol);2,2′-thiobis(4methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); derivatives of 2,2′- or4,4-biphenoldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tertbutylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol;2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiolsincluding 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); butylatedhydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol), bisphenolscomprising heteroatoms including2,6-di-tert-alpha-dimethylamino-p-cresol,4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including;bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and mixtures andcombinations thereof.

In some embodiments, the disclosed compositions contain at least onetracer. In some embodiments, the tracer additive in the disclosedcompositions consists of two or more tracer compounds from the sameclass of compounds or from different classes of compounds.

In some embodiments, the tracer component or tracer blend is present inthe compositions at a total concentration of about 50 parts per millionby weight (ppm) to about 1000 ppm. In other embodiments, the tracercompound or tracer blend is present at a total concentration of about 50ppm to about 500 ppm. In other embodiment, the tracer compound or tracerblend is present at a total concentration of about 100 ppm to about 300ppm.

In some embodiments, the disclosed compositions include at least onetracer selected from the group consisting of hydrofluorocarbons (HFCs),deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers,brominated compounds, iodated compounds, alcohols, aldehydes andketones, nitrous oxide and combinations thereof. Some embodiments of thedisclosed compositions include at least one tracer selected from thegroup consisting of fluoroethane, 1,1,-difluoroethane,1,1,1-trifluoroethane, 1,1,1,3,3,3-hexafluoropropane,1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,3,3-pentafluoropropane,1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane,1,1,1,2,2,3,4,5,5,6,6,7,7,7-tridecafluoroheptane,iodinetrifluoromethane, deuterated hydrocarbons, deuteratedhydrofluorocarbons, perfluorocarbons, fluoroethers, brominatedcompounds, iodated compounds, alcohols, aldehydes, ketones, nitrousoxide (N₂O) and mixtures thereof. In some embodiments, the traceradditive is a tracer blend containing two or more hydrofluorocarbons, orone hydrofluorocarbon in combination with one or more perfluorocarbons.

In some embodiments, at least one tracer composition is added to thedisclosed compositions in previously determined quantities to allowdetection of any dilution, contamination or other alteration of thecomposition.

In other embodiments, the compositions disclosed herein may furtherinclude a perfluoropolyether. A common characteristic ofperfluoropolyethers is the presence of perfluoroalkyl ether moieties.Perfluoropolyether is synonymous to perfluoropolyalkylether. Othersynonymous terms frequently used include “PFPE”, “PFAE”, “PFPE oil”,“PFPE fluid”, and “PFPAE”. In some embodiments, the perfluoropolyetherhas the formula of CF₃—(CF₂)₂—O—[CF(CF₃)—CF₂—O]j′-R′ f, and iscommercially available from DuPont under the trademark Krytox®. In theimmediately preceding formula, j′ is 2-100, inclusive and R′ f isCF₂CF₃, a C3 to C6 perfluoroalkyl group, or combinations thereof.

Other PFPEs, commercially available from Ausimont of Milan, Italy, andMontedison S.p.A., of Milan, Italy, under the trademarks Fomblin® andGalden®, respectively, and produced by perfluoroolefin photooxidation,can also be used.

PFPE commercially available under the trademark Fomblin®-Y can have theformula of CF₃O(CF₂CF(CF₃)—O—)_(m′)(CF₂—O—)_(n′)—R_(1f). Also suitableis CF₃O[CF₂CF(CF₃)O]_(m′)(CF₂CF₂O)_(O′)(CF₂O)_(n′—R) _(1f). In theformulae R_(1f) is CF₃, C₂F₅, C₃F₇, or combinations of two or morethereof; (m′+n′) is 8-45, inclusive; and m/n is 20-1000, inclusive; o′is 1; (m′+n′+o′) is 8-45, inclusive; m′/n′ is 20-1000, inclusive.

PFPE commercially available under the trademark Fomblin®-Z can have theformula of CF₃O(CF₂CF₂—O—)_(p′)(CF₂—O)_(q′)CF₃ where (p′+q′) is 40-180and p′/q′ is 0.5-2, inclusive.

Another family of PFPE, commercially available under the trademarkDemnum™ from Daikin Industries, Japan, can also be used. It can beproduced by sequential oligomerization and fluorination of2,2,3,3-tetrafluorooxetane, yielding the formula ofF—[(CF₂)₃—O]_(t′)—R_(2f) where R_(2f) is CF₃, C₂F₅, or combinationsthereof and t′ is 2-200, inclusive.

In some embodiments, the PFPE is unfunctionalized. In anunfunctionalized perfluoropolyether, the end group can be branched orstraight chain perfluoroalkyl radical end groups. Examples of suchperfluoropolyethers can have the formula ofC_(r′)F_((2r′+1))-A-C_(r′)F_((2r′+1)) in which each r′ is independently3 to 6; A can be O—(CF(CF₃)CF₂—O)_(w′), O—(CF₂O)_(x′)(CF₂CF₂—O)_(y′),O—(C₂F₄—O)_(w′), O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′),O—(CF(CF₃)CF₂—O)_(x′)(CF₂—O)_(y′), O—(CF₂CF₂CF₂—O)_(w′),O—(CF(CF₃)CF₂—O)_(x′)(CF₂CF₂—O)_(y′)—(CF₂—O)_(z), or combinations of twoor more thereof; preferably A is O—(CF(CF₃)CF₂—O)_(w′), O—(C₂F₄—O)^(w′),O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′),O—(CF₂CF₂CF₂—O)_(w)′, or combinations oftwo or more thereof; w′ is 4 to 100; x′ and y′ are each independently 1to 100. Specific examples include, but are not limited to,F(CF(CF₃)—CF₂—O)₉—CF₂CF₃, F(CF(CF₃)—CF₂—O)₉—CF(CF₃)₂, and combinationsthereof. In such PFPEs, up to 30% of the halogen atoms can be halogensother than fluorine, such as, for example, chlorine atoms.

In other embodiments, the two end groups of the perfluoropolyether,independently, may be functionalized by the same or different groups. Afunctionalized PFPE is a PFPE wherein at least one of the two end groupsof the perfluoropolyether has at least one of its halogen atomssubstituted by a group selected from esters, hydroxyls, amines, amides,cyanos, carboxylic acids, sulfonic acids or combinations thereof.

In some embodiments, representative ester end groups include —COOCH₃,—COOCH₂CH₃, CF₂COOCH₃, —CF₂COOCH₂CH₃, —CF₂CF₂COOCH₃, —CF₂CF₂COOCH₂CH₃,—CF₂CH₂COOCH₃, —CF₂CF₂CH₂COOCH₃, —CF₂CH₂CH₂COOCH₃, —CF₂CF₂CH₂CH₂COOCH₃.

In some embodiments, representative hydroxyl end groups include —CF₂OH,—CF₂CF₂OH, —CF₂CH₂OH, —CF₂CF₂CH₂OH, —CF₂CH₂CH₂OH, —CF₂CF₂CH₂CH₂OH.

In some embodiments, representative amine end groups include —CF₂NR¹R²,—CF₂CF₂NR¹R², —CF₂CH₂NR¹R², —CF₂CF₂CH₂NR¹R², —CF₂CH₂CH₂NR¹R²,—CF₂CF₂CH₂CH₂NR¹R², wherein R¹ and R² are independently H, CH₃, orCH₂CH₃.

In some embodiments, representative amide end groups include—CF₂C(O)NR¹R², —CF₂CF₂C(O)NR¹R², —CF₂CH₂C(O)NR¹R², —CF₂CF₂CH₂C(O)NR¹R²,—CF₂CH₂CH₂C(O)NR¹R², —CF₂CF₂CH₂CH₂C(O)NR¹R², wherein R¹ and R² areindependently H, CH₃, or CH₂CH₃.

In some embodiments, representative cyano end groups include —CF₂CN,—CF₂CF₂CN, —CF₂CH₂CN, —CF₂CF₂CH₂CN, —CF₂CH₂CH₂CN, —CF₂CF₂CH₂CH₂CN.

In some embodiments, representative carboxylic acid end groups include—CF₂COOH, —CF₂CF₂COOH, —CF₂CH₂COOH, —CF₂CF₂CH₂COOH, —CF₂CH₂CH₂COOH,—CF₂CF₂CH₂CH₂COOH.

In some embodiments, the sulfonic acid end groups is selected from thegroup consisting of —S(O)(O)OR³, —S(O)(O)R⁴, —CF₂OS(O)(O)OR³,—CF₂CF₂OS(O)(O)OR³, —CF₂CH₂OS(O)(O)OR³, —CF₂CF₂CH₂OS(O)(O)OR³,—CF₂CH₂CH₂OS(O)(O)OR³, —CF₂CF₂CH₂CH₂OS(O)(O)OR³, —CF₂S(O)(O)OR³,—CF₂CF₂S(O)(O)OR³, —CF₂CH₂S(O)(O)OR³, —CF₂CF₂CH₂S(O)(O)OR³,—CF₂CH₂CH₂S(O)(O)OR³, —CF₂CF₂CH₂CH₂S(O)(O)OR³, —CF₂OS(O)(O)R⁴,—CF₂CF₂OS(O)(O)R⁴, —CF₂CH₂OS(O)(O)R⁴, —CF₂CF₂CH₂OS(O)(O)R⁴,—CF₂CH₂CH₂OS(O)(O)R⁴, —CF₂CF₂CH₂CH₂OS(O)(O)R⁴, wherein R³ is H, CH₃,CH₂CH₃, CH₂CF₃, CF₃, or CF₂CF₃, R⁴ is CH₃, CH₂CH₃, CH₂CF₃, CF₃, orCF₂CF₃.

In some embodiments, the disclosed compositions include additives thatare members of the triaryl phosphate family of EP (extreme pressure)lubricity additives, such as butylated triphenyl phosphates (BTPP), orother alkylated triaryl phosphate esters, e.g. Syn-0-Ad® 8478 from AkzoChemicals, tricresyl phosphates and related compounds. Additionally, themetal dialkyl dithiophosphates (e.g., zinc dialkyl dithiophosphate (orZDDP), including the commercially available Lubrizol 1375 and othermembers of this family of chemicals is used in compositions of thedisclosed compositions. Other antiwear additives include natural productoils and asymmetrical polyhydroxyl lubrication additives, such as thecommercially available Synergol TMS (International Lubricants).

In some embodiments, stabilizers such as antioxidants, free radicalscavengers, and water scavengers and mixtures thereof are included. Suchadditives in this category can include, but are not limited to,butylated hydroxy toluene (BHT), epoxides, and mixtures thereof.Corrosion inhibitors include dodecyl succinic acid (DDSA), aminephosphate (AP), oleoyl sarcosine, imidazone derivatives and substitutedsulfphonates.

In one embodiment, the compositions disclosed herein may be prepared byany convenient method to combine the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

In another embodiment, the compositions disclosed herein may be preparedby a method comprising (i) reclaiming a volume of one or more componentsof a refrigerant composition from at least one refrigerant container,(ii) removing impurities sufficiently to enable reuse of said one ormore of the reclaimed components, (iii) and optionally, combining all orpart of said reclaimed volume of components with at least one additionalrefrigerant composition or component.

A refrigerant container may be any container in which is stored arefrigerant blend composition that has been used in a refrigerationapparatus, air-conditioning apparatus or heat pump apparatus. Saidrefrigerant container may be the refrigeration apparatus,air-conditioning apparatus or heat pump apparatus in which therefrigerant blend was used. Additionally, the refrigerant container maybe a storage container for collecting reclaimed refrigerant blendcomponents, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend orrefrigerant blend component that may be moved out of the refrigerantcontainer by any method known for transferring refrigerant blends orrefrigerant blend components.

Impurities may be any component that is in the refrigerant blend orrefrigerant blend component due to its use in a refrigeration apparatus,air-conditioning apparatus or heat pump apparatus. Such impuritiesinclude but are not limited to refrigeration lubricants, being thosedescribed earlier herein, particulates including but not limited tometal, metal salt or elastomer particles, that may have come out of therefrigeration apparatus, air-conditioning apparatus or heat pumpapparatus, and any other contaminants that may adversely effect theperformance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of therefrigerant blend or refrigerant blend component without adverselyeffecting the performance or equipment within which the refrigerantblend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend orrefrigerant blend component to the residual refrigerant blend orrefrigerant blend component in order to produce a composition that meetsthe specifications required for a given product. For instance, if arefrigerant blend has 3 components in a particular weight percentagerange, it may be necessary to add one or more of the components in agiven amount in order to restore the composition to within thespecification limits.

Compositions of the present invention have zero ozone depletionpotential and low global warming potential (GWP). Additionally, thecompositions of the present invention will have global warmingpotentials that are less than many hydrofluorocarbon refrigerantscurrently in use. One aspect of the present invention is to provide arefrigerant with a global warming potential of less than 1000, less than500, less than 150, less than 100, or less than 50.

Methods of Use

The compositions disclosed herein may be useful as low global warmingpotential (GWP) replacements for currently used refrigerants, includingbut not limited to R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22(or HCFC-22, chlorodifluoromethane), R12 (CFC-12,dichlorodifluoromethane); R407C (ASHRAE designation for a blend of 52weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23weight percent R32 (difluoromethane)); R410A (ASHRAE designation for ablend of 50 weight percent R125 and 50 weight percent R32); R417A(ASHRAE designation for a blend of 46.6 weight percent R125, 50.0 weightpercent R134a, and 3.4 weight percent n-butane); R419A (ASHRAEdesignation for a blend containing R125, R134a and DME); R422A, R422B,R422C and R422D (ASHRAE designation for blends of R125, R134a, isobutanein differing component concentrations); R404A (ASHRAE designation for ablend of 44 weight percent R125, 52 weight percent R143a(1,1,1-trifluoroethane), and 4.0 weight percent R134a); R413A (ASHRAEdesignation for a blend containing R218, R134a, and isobutane); R423A(ASHRAE designation for a blend containing 52.5 weight percent R134a and47.5 weight percent R227ea (1,1,1,2,3,3,3-heptafluoropropane)); R424A(ASHRAE designation for a blend containing R125, R134a, isobutane,n-butane, and isopentane); R426A (ASHRAE designation for a blendcontaining R125, R134a, n-butane, and isopentane); R428A (ASHRAEdesignation for a blend containing R125, R143a, propane and isobutane);R430A (ASHRAE designation for a blend containing R152a and isobutane);R434A (ASHRAE designation for a blend containing about 63.2 weightpercent R125, about 16 weight percent R134a, about 18 weight percentR143a, and about 2.8 weight percent isobutane); R437A (ASHRAEdesignation for a blend containing about 19.5 weight percent R125, about78.5 weight percent R134a, about 1.4 weight percent n-butane, and about0.6 weight percent n-pentane); R438A (ASHRAE designation for a blendcontaining about 8.5 weight percent R32, about 45 weight percent R125,about 44.2 weight percent R134a, about 1.7 weight percent n-butane, andabout 0.6 weight percent isopentane); and R507A (ASHRAE designation fora blend of 50 weight percent R125 and 50 weight percent R143a).Additionally, the compositions disclosed herein may be useful asreplacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAEdesignation for a blend of 51.2 weight percent CFC-115(chloropentafluoroethane) and 48.8 weight percent HCFC-22).

Often replacement refrigerants are most useful if capable of being usedin the original refrigeration equipment designed for a differentrefrigerant. In particular, the compositions as disclosed herein may beuseful as replacements for R12, R134a, R407C, R417A, and R422D, amongothers in original equipment. Additionally, the compositions asdisclosed herein may be useful as replacements for R410A, R507, R404A,502, and R422A, among others, in equipment designed for theserefrigerants with some system modifications. Further, the compositionsas disclosed herein may be useful for replacing any of the abovementioned refrigerants in equipment specifically modified for orproduced entirely for these new compositions

In many applications, some embodiments of the disclosed compositions areuseful as refrigerants and provide at least comparable coolingperformance (meaning cooling capacity and energy efficiency) as therefrigerant for which a replacement is being sought.

In some embodiments, the use of the above disclosed compositionsincludes using the composition as heat transfer compositions inprocesses to produce heat comprising condensing a composition asdisclosed herein in the vicinity of a body to be heated and thereafterevaporating said composition.

Also disclosed herein is the use of the above disclosed compositions asheat transfer compositions in processes to produce cooling comprisingcondensing a composition as disclosed herein and thereafter evaporatingsaid composition in the vicinity of a body to be cooled.

In some embodiments, the use of the above disclosed compositionsincludes using the composition as heat transfer compositions inprocesses for producing cooling, wherein the composition is first cooledand stored under pressure and when exposed to a warmer environment, thecomposition absorbs some of the ambient heat, expands, and the warmerenvironment is thusly cooled.

In another embodiment is provided a method for recharging a heattransfer system that contains a refrigerant to be replaced and alubricant, said method comprising removing the refrigerant to bereplaced from the heat transfer system while retaining a substantialportion of the lubricant in said system and introducing one of theherein disclosed compositions to the heat transfer system. In anotherembodiment, a heat exchange system comprising a composition disclosedherein is provided, wherein said system is selected from the groupconsisting of air conditioners, freezers, refrigerators, heat pumps,water chillers, flooded evaporator chillers, direct expansion chillers,walk-in coolers, heat pumps, mobile refrigerators, mobile airconditioning units, and systems having combinations thereof.Additionally, the compositions as disclosed herein may be useful insecondary loop systems wherein these compositions serve as the primaryrefrigerant thus providing cooling to a secondary heat transfer fluidthat thereby cools a remote location.

In another embodiment is provided a method for replacing a high GWPrefrigerant in a refrigeration, air-conditioning, or heat pumpapparatus, wherein said high GWP refrigerant is selected from the groupconsisting of R134a, R22, R12, R404A, R410A, R407C, R413A, R417A, R422A,R422B, R422C and R422D, R423A, R507A, R502, and R437A, said methodcomprising providing a composition as disclosed herein to saidrefrigeration, air-conditioning, or heat pump apparatus that uses, usedor is designed to use said high GWP refrigerant; wherein saidcomposition is selected from the group consisting of:

-   -   HFO-1234yf and cyclopropane;    -   HFO-1234yf and propylene;    -   HFO-1234yf, HFC-152a, and cyclopropane;    -   HFO-1234yf, HFC-152a, and propane; and    -   HFO-1234yf, HFC-134a, and cyclopropane.

In another embodiment, the method for replacing a high GWP refrigerantmay further comprise providing a composition to said refrigeration,air-conditioning, or heat pump apparatus that uses, used or is designedto use said high GWP refrigerant, wherein the composition is selectedfrom the group consisting of:

-   -   HFO-1234yf and cyclopropane;    -   HFO-1234yf and propylene;    -   HFO-1234yf, HFC-152a, and cyclopropane;    -   HFO-1234yf, HFC-152a, and propane; and    -   HFO-1234yf, HFC-134a, and cyclopropane.

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows. Liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator, by withdrawing heat from theenvironment, at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

In one embodiment, there is provided a heat transfer system containing acomposition as disclosed herein. In another embodiment is disclosed arefrigeration, air-conditioning or heat pump apparatus containing acomposition as disclosed herein. In another embodiment, is disclosed astationary refrigeration or air-conditioning apparatus containing acomposition as disclosed herein. In yet another embodiment is discloseda mobile refrigeration or air conditioning apparatus containing acomposition as disclosed herein.

In another embodiment, a method is provided for producing coolingcomprising evaporating any of the disclosed compositions in the vicinityof a body to be cooled, and thereafter condensing said composition.

In another embodiment, a method is provided for producing heatcomprising condensing any of the compositions as discloses herein in thevicinity of a body to be heated, and thereafter evaporating saidcompositions.

In another embodiment, disclosed is a method of using the composition ofthe present invention as a heat transfer fluid composition. The methodcomprises transporting said composition from a heat source to a heatsink.

In another embodiment, the present invention relates to foam expansionagent compositions comprising the fluoroolefin-containing compositionsof the present invention as described herein for use in preparing foams.In other embodiments the invention provides foamable compositions, andpreferably polyurethane and polyisocyanate foam compositions, and methodof preparing foams. In such foam embodiments, one or more of the presentfluoroolefin-containing compositions are included as a foam expansionagent in foamable compositions, which composition preferably includesone or more additional components capable of reacting and foaming underthe proper conditions to form a foam or cellular structure.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition afluoroolefin-containing composition of the present invention; and (b)reacting the foamable composition under conditions effective to form afoam.

Another embodiment of the present invention relates to the use of thefluoroolefin-containing compositions as described herein for use aspropellants in sprayable compositions. Additionally, the presentinvention relates to a sprayable composition comprising thefluoroolefin-containing compositions as described herein. The activeingredient to be sprayed together with inert ingredients, solvents andother materials may also be present in a sprayable composition.Preferably, the sprayable composition is an aerosol. Suitable activematerials to be sprayed include, without limitations, cosmeticmaterials, such as deodorants, perfumes, hair sprays, cleaners, andpolishing agents as well as medicinal materials such as anti-asthma andanti-halitosis medications.

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a fluoroolefin-containingcomposition as described herein to active ingredients in an aerosolcontainer, wherein said composition functions as a propellant.

EXAMPLES

The concepts disclosed herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1 Impact of Vapor Leakage

A vessel is charged with an initial composition at the indicatedtemperature, and the initial vapor pressure of the composition ismeasured. The composition is allowed to leak from the vessel, while thetemperature is held constant, until 50 weight percent of the initialcomposition is removed, at which time the vapor pressure of thecomposition remaining in the vessel is measured. Estimates are shown inTable 3.

TABLE 3 After After 50% 50% Composition Initial P Initial Leak LeakDelta P wt % (Psia) P (kPa) (Psia) (kPa) (%) HFO-1234yf/cyclopropane (at25° C.) 65.4/34.6 123.8 853.6 123.8 853.6 0.0% 80/20 121.8 839.8 120.4830.1 1.1% 90/10 115.6 797.0 111.9 771.5 3.2% 99/1 101.0 696.4 99.7687.4 1.3% 50/50 122.5 844.6 121.6 838.4 0.7% 30/70 117.9 812.9 114.6790.1 2.8% 10/90 110.2 759.8 107.5 741.2 2.5% 1/99 105.6 728.1 105.2725.3 0.4% HFO-1234yf/propylene (at 25° C.) 23.9/76.1 167.7 1156.3 167.71156.3 0.0% 10/90 167.1 1152.1 167.0 1151.4 0.1% 1/99 166.1 1145.2 166.11145.2 0.0% 40/60 166.8 1150.1 166.4 1147.3 0.2% 60/40 161.9 1116.3158.7 1094.2 2.0% 80/20 147.8 1019.1 136.6 941.8 7.6% 85/15 141.0 972.2127.4 878.4 9.6% 86/14 139.3 960.4 125.4 864.6 10.0% 87/13 137.6 948.7123.4 850.8 10.3% 95/5 118.1 814.3 106.7 735.7 9.7% 97/3 111.2 766.7103.0 710.2 7.4% 99/1 103.0 710.2 99.8 688.1 3.1%HFO-1234yf/HFC-152a/cyclopropane (at 25° C.) 52.6/11.1/36.3 124.4 857.7124.4 857.9 0.0% 98/1/1 101.2 697.8 99.9 688.8 1.3% 1/98/1 88.0 606.786.7 597.8 1.5% 1/1/98 106.5 734.3 105.6 728.1 0.8% 80/10/10 116.0 799.8112.5 775.7 3.0% 10/80/10 104.2 718.4 97.4 671.6 6.5% 10/10/80 116.3801.9 112.7 777.0 3.1% 60/20/20 121.6 838.4 119.9 826.7 1.4% 20/60/20115.3 795.0 110.7 763.3 4.0% 20/20/60 121.8 839.8 120.7 832.2 0.9%40/30/30 122.9 847.4 122.1 841.9 0.7% 30/40/30 121.5 837.7 120.2 828.81.1% 30/30/40 123.3 850.1 123.2 849.4 0.1% 10/40/50 121.6 838.4 121.4837.0 0.2% 50/40/10 112.8 777.7 108.3 746.7 4.0% 5/90/5 96.1 662.6 91.0627.4 5.3% 80/17/3 106.4 733.6 103.8 715.7 2.4% 60/37/3 104.5 720.5101.6 700.5 2.8% 15/70/15 110.5 761.9 104.2 718.4 5.7%HFO-1234yf/HFC-152a/propane (at zero ° C.) 18.2/27.5/54.3 76.0 524.076.0 524.0 0.0% 98/1/1 48.3 333.0 46.0 317.2 4.8% 1/98/1 46.4 319.9 38.7266.8 16.6% 1/1/98 69.4 478.5 69.1 476.4 0.4% 70/15/15 68.5 472.3 61.0420.6 10.9% 70/5/25 72.5 499.9 69.4 478.5 4.3% 80/5/15 68.1 469.5 61.0420.6 10.4% 50/25/25 72.9 502.6 69.5 479.2 4.7% 40/40/20 71.2 490.9 64.6445.4 9.3% 60/20/60 71.2 490.9 65.9 454.4 7.4% 40/20/40 75.4 519.9 74.9516.4 0.7% 30/10/60 75.6 521.2 75.4 519.9 0.3% 15/5/80 73.4 506.1 72.4499.2 1.4% 5/5/90 71.6 493.7 70.6 486.8 1.4%HFO-1234yf/134a/cyclopropane (at 25° C.) 98/1/1 101.4 699.1 100.0 689.51.4% 80/10/10 118.7 818.4 114.7 790.8 3.4% 70/15/15 123.9 854.3 121.1835.0 2.3% 60/20/20 127.4 878.4 125.8 867.4 1.3% 40/30/30 131.8 908.7131.2 904.6 0.5% 20/40/40 134.3 926.0 133.4 919.8 0.7% 10/45/45 135.1931.5 133.7 921.8 1.0% 1/49/50 135.7 935.6 133.4 919.8 1.7% 10/85/5117.3 808.8 107.7 742.6 8.2% 5/90/5 117.2 808.1 107.0 737.7 8.7% 1/98/1103.3 712.2 99.6 686.7 3.6% 1/1/98 106.8 736.4 105.4 726.7 1.3% 5/5/90113.2 780.5 107.5 741.2 5.0% 10/10/80 119.6 824.6 111.3 767.4 6.9%20/20/60 128.2 883.9 122.6 845.3 4.4% 80/17/3 109.7 756.4 106.3 732.93.1% 20/60/20 133.2 918.4 131.0 903.2 1.7%

Table 3 indicates which compositions are near azeotropic as thosecompositions wherein the difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent is removed is less than about 10 percent.

Example 2 Cycle Performance

Table 4 shows the cooling performance of various refrigerantcompositions as disclosed herein as compared to HFC-134a, HCFC-22,R407C, and HFO-1234yf. In the table, Evap Pres is evaporator pressure,Cond Pres is condenser pressure, Comp Exit T is compressor exittemperature, COP is coefficient of performance (analogous to energyefficiency), and Cap is cooling capacity. The data are based on thefollowing conditions:

Condenser Temperature 54° C. Evaporator Temperature  4° C. SubcoolTemperature  4° C. Return Gas Temperature 18° C. Compressor Efficiency70%

TABLE 4 Cond/ Comp Evap COP Cap Evap Cond exit average rel to rel toSuitable as pres, pres, temp, temp Cap, HFC- HFC- replacementComposition kPa kPa ° C. glide, ° C. COP kJ/m³ 134a 134a for . . .HFC-134a 337 1458 85.3 0 3.016 2184 100% 100% HCFC-22 565 2128 109.6 02.970 3402 98% 156% R-407C 558 2286 97.0 4.2 2.830 3302 94% 151%HFO-1234yf 359 1429 73.6 0 2.876 2026 95% 93% HFO-1234yf/ 379 1489 75.00.5 2.873 2124 95% 97% HFC-134a cyclopropane (97/3 wt %) HFO-1234yf/ 3901523 75.8 0.7 2.875 2182 95% 100% HFC-134a cyclopropane (95/5 wt %)HFO-1234yf/ 415 1590 77.6 0.8 2.887 2308 96% 106% HFC-134a cyclopropane(90/10 wt %) HFO-1234yf/ 465 1683 84.9 0 3.014 2642 100% 121% HCFC-22 orcyclopropane R407C (65.4/34.6 wt %) HFO- 388 1531 75.0 1.3 2.855 216095% 99% HFC-134a 1234yf/propylene (97/3 wt %) HFO- 406 1593 75.9 1.92.834 2239 94% 103% HFC-134a 1234yf/propylene (95/5 wt %) HFO- 448 172877.7 2.7 2.801 2414 93% 111% HFC-134a 1234yf/propylene (90/10 wt %) HFO-333 2256 89.0 0 2.860 3401 95% 156% HCFC-22 or 1234yf/propylene R407C(23.9/76.1 wt %) HFO-1234yf/HFC- 380 1503 79.3 0.4 2.934 2212 97% 101%HFC-134a 152a/cyclopropane (80/17/3 wt %) HFO-1234yf/HFC- 399 1565 87.01.1 3.004 2408 100% 110% HFC-134a 152a/cyclopropane (50/40/10 wt %)HFO-1234yf/ 496 1928 86.2 4.3 2.911 2862 97% 131% HCFC-22 or HFC-152aR407C (40/40/20 wt %) HFO-1234yf/HFC- 540 2025 83.2 2.5 2.815 2902 93%133% HCFC-22 or 152a/propane R407C (50/25/25 wt %) HFC-1234yf/HFC- 3881542 76.8 0.6 2.897 2222 96% 102% HFC-134a 134a/cyclopropane (80/17/3 wt%) HFC-1234yf/HFC- 423 1626 78.6 0.9 2.896 2371 96% 109% HFC-134a134a/cyclopropane (80/10/10 wt %)

It should be noted that all the blends as listed above have highercooling capacity than pure HFO-1234yf. Additionally, most blends haveless glide than R407C (an accepted refrigerant blend used at the presenttime). Finally, it can be seen that the various blends are potentialreplacements for HFC-134a, HCFC-22, or R407C as indicated in Table 4.

Example 3 Global Warming Potentials

Values for global warming potential (GWP) for certain disclosedcompositions are given in Table 5. The GWP for the pure components arelisted for reference. The values for HFCs and hydrocarbons are takenfrom the “Climate Change 2007—IPCC (Intergovernmental Panel on ClimateChange) Fourth Assessment Report on Climate Change”, from the sectionentitled “Working Group 1 Report: “The Physical Science Basis”, Chapter2, pp. 212-215, Tables 2.14 and 2.15. The value for HFO-1234yf andHFO-1234ze were published in Papadimitriou et al., Physical ChemistryChemical Physics, 2007, vol. 9, pp. 1-13. An estimated value for GWP=3(*) for cyclopropane is used as there is no value listed in the tablesreferenced herein. Specifically the 100 year time horizon values areused. The GWP values for compositions containing more than one componentare calculated as weighted averages of the individual component GWPvalues.

TABLE 5 Component or composition GWP Comparative HCFC-22 1810 HFC-32 675 HFC-134a 1430 HFC-125 3500 HFC-227ea 3220 cyclopropane   3* propane   3.3 propylene    1.8 n-butane   4 isobutane    4** dimethyl ether   1HFO-1234yf   4 R404A 3922 R407C 1802 R410A 2088 R417A 2346 R419A 2969R422D 2729 R423A 2281 R428A 3617 R437A 1806 R438A 2264 Compositions asdisclosed herein HFO-1234yf/cyclopropane (97/3 wt %)    4.0HFO-1234yf/cyclopropane (95/5 wt %)    4.0 HFO-1234yf/cyclopropane(90/10 wt %)    3.9 HFO-1234yf/cyclopropane (65.4/34.6 wt %)    3.7HFO-1234yf/propylene (97/3 wt %)    3.9 HFO-1234yf/propylene (95/5 wt %)   3.9 HFO-1234yf/propylene (90/10 wt %)    3.8 HFO-1234yf/propylene(23.9/76.1 wt %)    2.3 HFO-1234yf/HFC-152a/cyclopropane (80/17/3 wt %) 24 HFO-1234yf/HFC-152a/cyclopropane (50/40/10 wt %)  52HFO-1234yf/HFC-152a/cyclopropane (52.6/11.1/36.3 wt %)  17HFO-1234yf/HFC-152a/propane (40/40/20 wt %)  52HFO-1234yf/HFC-152a/propane (50/25/25 wt %)  34HFO-1234yf/HFC-152a/propane (18.2/27.5/54.3 wt %)  38HFO-1234yf/HFC-134a/cyclopropane (80/17/3 wt %)  246HFO-1234yf/HFC-134a/cyclopropane (80/10/10 wt %)  147 estimated GWPvalue for cyclopropane. **estimated GWP value for isobutane based onvalue for n-butane.

The GWP values for the compositions as disclosed herein listed above arelower than those for HFC-134a and HCFC-22 as well as the currently usedrefrigerant blends, R404A, R407C, R410A, and others as listed in thetable above.

1. A composition selected from the group consisting of compositionscomprising: HFO-1234yf and cyclopropane; HFO-1234yf and propylene;HFO-1234yf, HFC-152a, and cyclopropane; HFO-1234yf, HFC-152a, andpropane; and HFO-1234yf, HFC-134a, and cyclopropane.
 2. The compositionof claim 1 comprising a near-azeotropic composition comprising: about 1weight percent to about 99 weight percent HFO-1234yf and about 99 weightpercent to about 1 weight percent cyclopropane; about 1 weight percentto about 86 weight percent HFO-1234yf, about 99 weight percent to about14 weight percent propylene; about 95 weight percent to about 99 weightpercent HFO-1234yf, about 5 weight percent to about 1 weight percentpropylene; about 1 weight percent to about 98 weight percent HFO-1234yf,about 1 weight percent to about 98 weight percent HFC-152a, and about 1weight percent to about 98 weight percent cyclopropane; about 1 weightpercent to about 98 weight percent HFO-1234yf, about 1 weight percent toabout 98 weight percent HFC-152a, and about 20 weight percent to about98 weight percent propane; and about 1 weight percent to about 98 weightpercent HFO-1234yf; about 1 weight percent to about 98 weight percentHFC-134a, and about 1 weight percent to about 98 weight percentcyclopropane.
 3. The composition of claim 1 comprising an azeotropiccomposition comprising: about 65.4 weight percent HFC-1234yf and about34.6 weight percent cyclopropane at 25° C. and about 123.8 psia (kPa);about 23.9 weight percent HFO-1234yf and about 76.1 weight percentpropylene at 25° C. and about 167.7 psia (kPa); about 52.6 weightpercent HFO-1234yf, about 11.1 weight percent HFC-152a, and about 36.3weight percent cyclopropane at 25° C. and about 124.4 psia (kPa); andabout 18.2 weight percent HFO-1234yf, about 27.5 weight percentHFC-152a, and about 54.3 weight percent propane at about zero ° C. andabout 76.0 psia (kPa).
 4. The composition of claim 1 further comprisingat least one lubricant selected from the group consisting of mineraloils, alkylbenzenes, polyalphaolefins, polyalkylene glycols, polyolesters, polyvinyl ethers, and mixtures thereof.
 5. The compositions ofclaim 1 further comprising at least one additive selected from the groupconsisting of acetates, borates, carbonates, bicarbonates, phosphates,nitrates, hydroxides, oxides, molybdates, bromides, bromates, chlorates,chlorides, or iodides, phosphate esters, organic phosphonates, andphosphonium salts, boric acid, organic boron compounds, brominatedcompounds, chlorinated paraffins, ammonium polyphosphates, melamines,mixtures of water with polyalkylene glycols or polyol esters,perfluorinated lubricants, fluoroketones, fluoroiodo compounds, ormixtures thereof.
 6. A process to produce cooling comprising condensinga composition of claim 1 and thereafter evaporating said composition inthe vicinity of a body to be cooled.
 7. A process to produce heatcomprising condensing the composition of claim 1 in the vicinity of abody to be heated and thereafter evaporating said composition.
 8. Amethod for replacing R134a, R22, R12, R404A, R410A, R407C, R413A, R417A,R422A, R422B, R422C and R422D, R423A, R424A, R426A, R428A, R430A, R434A,R437A, R438A, R507A, R502, and R437A in a system that uses, used or wasdesigned to use R134a, R22, R12, R404A, R410A, R407C, R413A, R417A,R422A, R422B, R422C and R422D, R423A, R424A, R426A, R428A, R430A, R434A,R437A, R438A, R507A, R502, and R437A, wherein said method comprisesproviding the composition of claim 1 to said system.
 9. A refrigeration,air-conditioning or heat pump apparatus containing the composition ofclaim
 1. 10. A stationary air conditioning apparatus containing thecomposition of claim
 1. 11. A stationary refrigeration system containingthe composition of claim
 1. 12. A foam blowing agent comprising thecomposition of claim
 1. 13. A method of forming a foam comprising: (a)adding to a foamable composition the composition of claim 1; and (b)reacting the foamable composition under conditions effective to form afoam.
 14. A sprayable composition comprising the composition of claim 1.15. A process for producing aerosol products comprising the step ofadding the composition of claim 1 to active ingredients in an aerosolcontainer, wherein said composition functions as a propellant.